JP7071262B2 - Curable composition, method for producing cured product, and cured product thereof - Google Patents

Description

The present invention relates to a curable composition, a method for producing a cured product, and a cured product thereof, and more particularly to a curable composition having excellent adhesion to the cured product, a method for producing a cured product, and the cured product thereof.

Curable compositions are used in the fields of inks, paints, various coatings, adhesives, optical members and the like. Various reports have been made on such improvements in the curable composition.

For example, Patent Documents 1 to 4 propose various photocurable adhesives. Specifically, in Patent Document 1, a polyvinyl alcohol-based polarizing element and various protective films can be easily and firmly adhered with the same photocurable adhesive, substantially free of organic solvents, and a thin film with low viscosity. A photocurable adhesive having excellent coatability has been proposed. Further, Patent Document 2 proposes a photocurable epoxy resin-based adhesive that does not require irradiation with light having a very strong illuminance or heating after irradiation with light. Further, in Patent Document 3, a photocurable adhesive which has excellent storage stability, can suppress discoloration of the adhesive itself and the object to be bonded at the time of curing, has a high curing speed, and provides good adhesiveness. Proposed. Further, Patent Document 4 proposes a cationically polymerizable composition excellent in curability, adhesiveness and water resistance, and excellent in adhesive use.

Japanese Unexamined Patent Publication No. 2011-236389 Japanese Unexamined Patent Publication No. 2012-149262 International Publication No. 2008/111584 International Publication 2015/005211

However, even the adhesives proposed in Patent Documents 1 to 4 are not always satisfactory in terms of the adhesion of the cured product, and further studies are desired regarding the adhesion of the cured product. is the current situation.

Therefore, an object of the present invention is to provide a curable composition having excellent adhesion of the cured product, a method for producing the cured product, and the cured product thereof.

As a result of diligent studies to solve the above problems, the present inventors have found that a curable composition having a specific composition can solve the above problems, and have completed the present invention.

That is, the curable composition of the present invention is a curable composition containing 100 parts by mass of a cationically polymerizable component (A) and 1 to 10 parts by mass of a cationic polymerization initiator (B).
The cationically polymerizable component (A) has an aromatic epoxy compound (A1), an aliphatic glycidyl compound (A2), an oxetane compound (A3), and a cationically polymerizable substituent, and has a weight average molecular weight of 1,000 to 30. The aromatic epoxy compound (A1) is the main component of the cationically polymerizable component (A), and the polymer (A4) which is 000 is an essential component, and the polyfunctional aromatic epoxy compound and the monofunctional aromatic compound. Contains epoxy compounds,
The polymer (A4) having a cationically polymerizable substituent and having a weight average molecular weight of 1,000 to 30,000 monopolymerizes or monopolymerizes a compound having a cationically polymerizable substituent on the side chain and having an ethylenically unsaturated bond. It is obtained by copolymerization, and the cationically polymerizable substituent is an epoxy group or an oxetane group.
The monofunctional aromatic epoxy compound in the aromatic epoxy compound (A1) is characterized in that it is 30 to 50 parts by mass with respect to 100 parts by mass of the polyfunctional aromatic epoxy compound.

In the curable composition of the present invention, it is preferable to further contain the alicyclic epoxy compound (A5) as the cationically polymerizable component (A). Further, in the curable composition of the present invention, the oxetane compound (A3) is preferably a polyfunctional oxetane compound.

The method for producing a cured product of the present invention is characterized in that the curable composition of the present invention is irradiated with active energy rays or heated.

The cured product of the present invention is characterized by being a cured product of the curable composition of the present invention.

According to the present invention, it is possible to provide a curable composition having excellent adhesion of a cured product, a method for producing a cured product, and a cured product thereof. The curable composition of the present invention is useful for adhesives, particularly adhesives for polarizing plates.

Hereinafter, the curable composition of the present invention will be described in detail.
The curable composition of the present invention causes a polymerization or cross-linking reaction by a cationic polymerization initiator activated by energy ray irradiation or heating, and has 100 parts by mass of a cationically polymerizable component (A) and cationic polymerization. It contains 1 to 10 parts by mass of the initiator (B). In the curable composition of the present invention, the cationically polymerizable component (A) contains an aromatic epoxy compound (A1), an aliphatic glycidyl compound (A2), an oxetane compound (A3), and a cationically polymerizable substituent. The polymer (A4) having a weight average molecular weight of 1,000 to 30,000 is an essential component, and the aromatic epoxy compound (A1) is the main component of the cationically polymerizable component (A). In addition, an alicyclic epoxy compound (A5), a vinyl ether compound (A6) and the like may be contained. Here, the main component means a mixture of several types of cationically polymerizable components and the largest total of the same type of cationically polymerizable components.

The aromatic epoxy compound (A1) refers to an epoxy compound containing an aromatic ring, and the curable composition of the present invention contains both a polyfunctional aromatic epoxy compound and a monofunctional aromatic epoxy compound.

As a monofunctional aromatic epoxy compound, a phenol compound such as phenol, cresol, butylphenol or a monoglycidyl ether of an alkylene oxide adduct thereof; a monoglycidyl of an aromatic compound having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol. Aether compound; Monoglycidyl ether compound of an aromatic compound having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid. Monoglycidyl ester of a polybasic acid aromatic compound having; glycidyl ester of benzoic acid, monoepoxidized product of styrene oxide or divinylbenzene and the like can be mentioned.

Examples of the polyfunctional aromatic epoxy compound include polyhydric phenol having at least one aromatic ring such as bisphenol A and bisphenol F, or a polyglycidyl etherified product of an alkylene oxide adduct thereof; epoxynovolac resin; resorcinol, hydroquinone, catechol and the like. Polyglycidyl etherified product of an aromatic compound having two or more phenolic hydroxyl groups; Polyglycidyl etherified product of an aromatic compound having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, and phenyldibutanol; , Polyglycidyl ester of a polybasic acid aromatic compound having two or more carboxylic acids such as terephthalic acid and trimellitic acid; and a diepoxide of divinylbenzene and the like.

The ratio of the polyfunctional aromatic epoxy compound to the monofunctional aromatic epoxy compound is 20 to 50 parts by mass, particularly 30 to 40 parts by mass, with respect to 100 parts by mass of the polyfunctional aromatic epoxy compound. Is preferable from the viewpoint of low viscosity, coatability and reactivity.

As the aromatic epoxy compound (A1), commercially available products can be used, for example, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-. 721, On-Coat EX-1020, On-Coat EX-1030, On-Coat EX-1040, On-Coat EX-1050, On-Coat EX-1051, On-Coat EX-1010, On-Coat EX-1011, On-Coat 1012 (Nagasechem) Tex Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (manufactured by DIC Co., Ltd.) ); ESN-475V (manufactured by Nippon Steel & Sumitomo Metal Corporation); Epicoat YX8800 (manufactured by Mitsubishi Chemical Co., Ltd.); Marproof G-0105SA, Marproof G-0130SP (manufactured by Nichiyu Co., Ltd.); Epicron N-665, Epicron HP-7200 (manufactured by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN -502H, NC-7000L (manufactured by Nippon Kayaku Co., Ltd.); Adeka Glycyllol ED-509s, Adeka Glycyllol ED-501, Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (Manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Printec Co., Ltd.) and the like. As the aromatic epoxy compound (A1), a polyfunctional compound is preferable because it has excellent curability.

The viscosity, coatability, reactivity and curability of the aromatic epoxy compound (A1) are 20 to 80 parts by mass, particularly 30 to 50 parts by mass with respect to 100 parts by mass of the cationically polymerizable component (A). Is preferable because it improves. As described above, the main component is a mixture of several types of cationically polymerizable components, and the total amount of the same type of cationically polymerizable components is the largest.

The aliphatic glycidyl compound (A2) refers to an epoxy compound that is not classified into the above-mentioned aromatic epoxy compound (A1) and the later-described alicyclic epoxy compound (A5), and specific examples of the aliphatic glycidyl compound (A2) include , Polyglycidyl etherified compounds of aliphatic alcohols, polyglycidyl etherified compounds of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, monofunctional epoxy compounds such as glycidyl esters of alkylcarboxylic acids. Examples thereof include polyfunctional epoxy compounds such as. Typical compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl. Polyvalents such as glycol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, etc. Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycidyl ethers of alcohols, propylene glycol, trimethylolpropane, and glycerin, and aliphatic long chains. Diglycidyl ester of dibasic acid can be mentioned. Further, monoglycidyl ether of an aliphatic higher alcohol, glycidyl ester of a higher fatty acid, epoxidized soybean oil, octyl epoxidate stearate, butyl epoxidized stearate, epoxidized soybean oil, epoxidized polybutadiene and the like can be mentioned.

As the aliphatic glycidyl compound (A2), a glycidyl etherified product of an aliphatic alcohol or a polyglycidyl etherified product of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof is preferable because the viscosity, coatability and reactivity are improved.

As the aliphatic glycidyl compound (A2), a commercially available product can be used, for example, Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-221, Denacol EX-212, Denacol EX-. 313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX- 622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX- 911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glycyllol ED-503, Adeka Glycyllol ED-503G, Adeka Glycyllol ED-506, Adeka Glycyllol ED- 523T, ADEKA REGIN EP-4088S, ADEKA REGIN EP-4080E (manufactured by ADEKA Corporation) and the like can be mentioned.

The viscosity, coatability and reactivity of the aliphatic glycidyl compound (A2) are improved by 1 to 70 parts by mass, particularly 10 to 30 parts by mass with respect to 100 parts by mass of the cationically curable component (A). Therefore, it is preferable.

The oxetane compound (A3) contains either a polyfunctional oxetane compound containing two or more oxetane groups in the same molecule and a monofunctional oxetane compound containing one oxetane group in the same molecule. Examples of the oxetane compound (A3) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 1,2-bis. [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1 , 6-Bis (3-ethyl-3-oxetanylmethoxy) hexane and other polyfunctional oxetane compounds, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3 Examples thereof include monofunctional oxetane compounds such as -ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, and 3-ethyl-3- (chloromethyl) oxetane. These can be used alone or in combination of two or more, and a polyfunctional oxetane compound is preferable because the curability and adhesion of the cured product are improved.

As the oxetane compound (A3), a commercially available product can be used, for example, Aron oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-221, OXT-212 (Toagosei). (Manufactured by Ube Corporation), Etanacol OXBP, OXTP (manufactured by Ube Kosan Co., Ltd.) and the like.

The amount of the oxetane compound (A3) is preferably 1 to 70 parts by mass, particularly 10 to 40 parts by mass with respect to 100 parts by mass of the cationically curable component (A), because the viscosity, coatability and reactivity are improved. ..

A polymer (A4) having a weight average molecular weight of 1,000 to 30,000 having a cationically polymerizable substituent (hereinafter, also referred to as “polymer (A4)”) may have a cationically polymerizable substituent in the side chain. The skeleton of the main chain is not particularly limited, but a compound having an ethylenically unsaturated bond is preferably monopolymerized or copolymerized. The cationically polymerizable substituent represents an epoxy group or an oxetane group.

The polymer (A4) is a copolymer of a monomer represented by the following general formula (I), a copolymer of a plurality of monomers represented by the following general formula (I), and the following general formula. A monopolymer of the monomer represented by (II), a copolymer of a plurality of monomers represented by the following general formula (I), and a monomer represented by the following general formula (I). And the one obtained by copolymerizing the monomer represented by the following general formula (II).

ここで、式中、Ｘは、炭素原子数１～７のアルキル基、炭素原子数１～７のアルコキシ基、炭素原子数６～１２のアリール基、炭素原子数６～１２のアリールオキシ基もしくは炭素原子数６～１０の脂環式炭化水素基、またはこれらの基中の水素原子が、エポキシ基およびオキセタン基からなる群より選択される１種以上の基で置換されたものである。

Here, in the formula, X is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or An alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a hydrogen atom in these groups is substituted with one or more groups selected from the group consisting of an epoxy group and an oxetane group.

式中、Ｒ^１は、水素原子、メチル基またはハロゲン原子を表し、Ｘ’は、炭素原子数１～７のアルキル基、炭素原子数６～１２のアリール基もしくは炭素原子数６～１０の脂環式炭化水素基、またはこれらの基中の水素原子が、エポキシ基およびオキセタン基からなる群より選択される１種以上の基で置換されたものである。

In the formula, R ¹ represents a hydrogen atom, a methyl group or a halogen atom, and X'is an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms or a fat having 6 to 10 carbon atoms. A cyclic hydrocarbon group, or a hydrogen atom in these groups, is substituted with one or more groups selected from the group consisting of epoxy groups and oxetane groups.

Examples of the alkyl group having 1 to 7 carbon atoms represented by X in the formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, and iso. -Amil, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl and the like. Among these, an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms partially substituted with one or more groups selected from the group consisting of an epoxy group and an oxetane group is used. , Preferred from the viewpoint of curability.

Examples of the alkoxy group having 1 to 7 carbon atoms represented by X in the formula (I) include methoxy, ethoxy, propyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy and amyloxy. , Iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert -Heptyloxy and the like can be mentioned. Among these, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms partially substituted with one or more groups selected from the group consisting of an epoxy group and an oxetane group is used. , Preferred from the viewpoint of curability.

Examples of the aryl group having 6 to 12 carbon atoms represented by X in the formula (I) include phenyl, methylphenyl, naphthyl and the like.

Examples of the aryloxy group having 6 to 12 carbon atoms represented by X in the formula (I) include phenyloxy, methylphenyloxy, and naphthyloxy.

Examples of the alicyclic hydrocarbon group represented by X in the formula (I) having 6 to 10 carbon atoms include cyclohexyl, methylcyclohexyl, norbornyl, bicyclopentyl, bicyclooctyl, trimethylbicycloheptyl, and tricyclooctyl. Examples thereof include tricyclodecanyl, spirooctyl, spirobicyclopentyl, adamantyl, isobornyl and the like.

In the formula (I), when a part of X is substituted with an epoxy group or an oxetane group, the monomer represented by the formula (I) is, for example, the following formulas (1) to (3). Examples include the represented monomer.

式中、Ｒ^２は、水素原子または炭素原子数１～６のアルキル基を表し、ｍは、１～６の整数である。

In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6.

式中、Ｒ^３は、水素原子または炭素原子数１～６のアルキル基を表し、ｎは、１～６の整数である。

In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.

式中、Ｒ^４は、水素原子または炭素原子数１～６のアルキル基を表し、ｓは、１～６の整数である。

In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6.

In the formula (II), examples of the halogen atom represented by R ¹ include fluorine, chlorine, bromine, iodine and the like.

In the formula (II), when a part of X'is substituted with an epoxy group or an oxetane group, the monomer represented by the formula (II) is represented by the following formulas (4) to (6). What is done is mentioned.

式中、Ｒ^１は、上記式（ＩＩ）と同じであり、Ｒ^５は、水素原子または炭素原子数１～６のアルキル基を表し、ｔは、１～６の整数である。

In the formula, R ¹ is the same as the above formula (II), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6.

式中、Ｒ^１は、上記式（ＩＩ）と同じであり、Ｒ^６は、水素原子または炭素原子数１～６のアルキル基を表し、ｑは、１～６の整数である。

In the formula, R ¹ is the same as the above formula (II), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and q is an integer of 1 to 6.

式中、Ｒ^１は、上記式（ＩＩ）と同じであり、Ｒ^７は、水素原子または炭素原子数１～６のアルキル基を表し、ｙは、１～６の整数である。

In the formula, R ¹ is the same as the above formula (II), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6.

In the polymer (A4), the ratio of the monomers constituting the polymer is such that X is substituted with one or more groups selected from the group consisting of an epoxy group and an oxetane group, and the number of carbon atoms is 1 to 7. The monomer represented by (I) or (II) above is the above-mentioned monomer represented by (I) or (II) in the case of an alkyl group, an aryl group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms. It is preferable to use it so that it is 10 to 100% by mass with respect to the total 100% by mass of the monomers constituting the polymer because the adhesion is improved.

When an ethylenically unsaturated compound having a hydroxyl group or a carboxyl group is used in combination with the monomer represented by (I) or (II) as the monomer constituting the polymer (A4), the adhesion is improved. preferable.

The polymer (A4) is preferably 1 to 20 parts by mass, particularly 3 to 10 parts by mass with respect to 100 parts by mass of the cationically curable component (A) because the viscosity, coatability and reactivity are improved. ..

The alicyclic epoxy compound (A5) refers to a compound in which an oxylan ring is directly bonded to a saturated ring without a bonding group, and specific examples of the alicyclic epoxy compound include at least one alicyclic. Examples thereof include a polyglycidyl etherified product of a polyhydric alcohol having a formula ring or a cyclohexene oxide or a cyclopentene oxide-containing compound obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. For example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxy Cyclohexyl Methyl-6-Methyl-3,4-Epoxy Cyclohexanecarboxylate, 3,4-Epoxy-3-Methyl Cyclohexyl Methyl-3,4-Epoxy-3-Methyl Cyclohexanecarboxylate, 3,4-Epoxy-5 -Methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxy) Cyclohexane), Propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadienediepoxyside, ethylenebis (3,4-epoxy) Cyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinen Examples thereof include oxidase and limonendioxide. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate or 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate. It is preferable from the viewpoint of improving adhesion.

As the alicyclic epoxy compound (A5), a commercially available product can be used, and examples thereof include celoxide 2021P, celoxide 2081, celoxide 2000, and celoxide 3000 (manufactured by Daicel Corporation).

The viscosity, coatability and reactivity of the alicyclic epoxy compound (A5) are 0 to 30 parts by mass, particularly 0 to 20 parts by mass with respect to 100 parts by mass of the cationically curable component (A). It is preferable because it improves.

Examples of the vinyl ether compound (A6) include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, and triethylene glycol vinyl ether. Examples thereof include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,6-cyclohexanedimethanol divinyl ether.

The cationic polymerization initiator (B) according to the curable composition of the present invention may be any compound as long as it can release a substance that initiates cationic polymerization by irradiation with energy rays or heating. , Preferably a double salt, which is an onium salt that releases Lewis acid upon irradiation with energy rays, or a derivative thereof. Typical examples of such compounds include the following general formulas.
[A] ^{r +} [B] ^r-
Can be mentioned as cation and anion salts represented by.

Here, the cation [A] ^{r +} is preferably onium, and its structure is, for example, the following general formula.
[(R ⁸ ) _a Q] ^{r +}
Can be represented by.

Further, here, R ⁸ is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5. The a ^R8s are independent of each other and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{r +} is q, it is necessary that the relationship r = a−q is established (however, N = N is treated as having a valence of 0).

Further, the anion [B] ^r- is preferably a halide complex, and its structure is, for example, the following general formula.
[LY _b ] ^r-
Can be represented by.

Further, here, L is a metal or metalloid that is the central atom of the halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. Y is a halogen atom. b is an integer of 3 to 7. Further, when the valence of L in the anion [B] ^r- is p, it is necessary that the relationship r = bp is established.

Specific examples of the general anion [LY _b ] ^r- include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ^- , and hexa. Fluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^-and the like can be mentioned.

Further, the anion [B] ^r- is expressed by the following general formula,
[LY _b-1 (OH)] ^r-
The structure represented by is also preferably used. L, Y, b are the same as above. Other anions that can be used include perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , and toluene sulfonic acid anion. , Trinitrobenzene sulfonic acid anion, camphor sulphonate, nonafluorobutane sulphonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis (pentafluorophenyl) borate and the like.

In the curable composition of the present invention, it is particularly effective to use the following aromatic onium salts (a) to (c) among such onium salts. From these, one of them can be used alone, or two or more of them can be mixed and used.

(A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate and the like.

(B) Diaryl such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, trilcmil iodonium tetrakis (pentafluorophenyl) borate, etc. Iodium salt

(C) Sulfonium cations represented by Group I or Group II below and sulfonium salts such as hexafluoroantimon ion, hexafluorophosphate ion, and tetrakis (pentafluorophenyl) borate ion.

<Group I>

<Group II>

In addition, other preferable ones are (η ^5-2,4 -cyclopentadiene-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-allene complex such as hexafluorophosphate, aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salitylaldehidat) aluminum, and silanols such as triphenylsilanol. Mixtures of; salts such as thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino Alicyclic polyamines such as -3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylene diamine, diaminodiphenylmethane and diaminodiphenylsulfone; the above polyamines and phenylglycidyl ether, butylglycidyl ether, Polyepoxy addition modified product produced by reacting with various epoxy resins such as glycidyl ethers such as bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acid by a conventional method; the above organic Amidation modified products produced by reacting polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by a conventional method; Mannich's modified product produced by reacting a nucleus such as tributylphenol and resorcin with at least one phenol having an aldehyde oxidation-reactive site by a conventional method; polyvalent carboxylic acid (succinic acid, malonic acid, succinic acid). , Glutalic acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyl Aliphatic dicarboxylic acids such as octanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid; phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and the like. Aromatic dicarboxylic acids; cyclohexanedicarbo Acid anhydrides of alicyclic dicarboxylic acids such as acids; tricarboxylic acids such as trimellitic acid, trimesic acid, trimer of castor oil fatty acid; tetracarboxylic acids such as pyromellitic acid; dicyandiamide, imidazole, carboxylic acid ester , Sulphonic acid ester, amineimide and the like.

Among these, from the viewpoint of practical use and improvement of photosensitivity, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex, and an aromatic sulfonium salt having the following structure is used as a cationic polymerization initiator (B). ) It is more preferable to contain at least 0.1% by mass with respect to 100% by mass.

ここで、式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９およびＲ^２０は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基または炭素原子数２～１０のエステル基を表し、Ｒ^２１、Ｒ^２２、Ｒ^２３およびＲ^２４は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数１～１０のアルキル基を表し、Ｒ^２５は、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基または下記化学式（Ａ）～（Ｃ）より選択されるいずれかの置換基を表し、Ａｎ^ｑ－はｑ価の陰イオンを表し、ｐは電荷を中性にする係数を表す。

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently hydrogen atom, halogen atom and carbon atom number, respectively. Represents an alkyl group of 1 to 10, an alkoxy group having 1 to 10 carbon atoms, or an ester group having 2 to 10 carbon atoms, and R ²¹ , R ²² , R ²³ , and R ²⁴ are independently hydrogen atoms and halogens, respectively. Represents an atom or an alkyl group having 1 to 10 carbon atoms, and ^R25 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any of the following chemical formulas (A) to (C). Represents a substituent, An ^q- represents a q-valent anion, and p represents a coefficient that neutralizes the charge.

ここで、式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８およびＲ^３９は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基または炭素原子数２～１０のエステル基を表し、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数１～１０のアルキル基を表し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８およびＲ^３９で表される基の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、メルカプト基、イソシアネート基、複素環含有基で置換されていてもよく、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８およびＲ^３９で表される基中のメチレン基は－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｓ－、－ＳＯ_２－、－ＳＣＯ－または－ＣＯＳ－で置換されていてもよい。

Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ . , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are independently hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms and 1 carbon atom, respectively. Represents an alkoxy group of up to 10 or an ester group of 2 to 10 carbon atoms, and R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ independently represent a hydrogen atom, a halogen atom or an ester group having 1 to 10 carbon atoms, respectively. Represents the alkyl groups of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ . , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are the hydrogen atoms of the groups represented by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups and carboxyl groups. , Methacryloyl group, acryloyl group, epoxy group, vinyl group, mercapto group, isocyanate group, heterocyclic-containing group may be substituted with R11, ^R12 , ^R13 , ^R14 , ^R15 , ^R16 , ^{R. 17} , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ . The methylene group in the represented group may be substituted with -O-, -CO-, -COO-, -OCO-, -S-, -SO _2- , -SCO- or -COS-.

Among the compounds represented by the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ . , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ . Examples of the halogen atom to be formed include fluorine, chlorine, bromine, iodine and the like.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ . , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ as alkyl groups with 1-10 carbon atoms. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, Examples include decyl and isodecyl.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ . , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ , as alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, s-butyloxy. t-butyloxy, isobutyloxy, pentyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethyloxy, 3-methoxypropyloxy, 4- Examples thereof include methoxybutyloxy, 2-butoxyethyloxy, methoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, trifluoromethyloxy and the like.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁶ , R ²⁷ , R ²⁸ . , R ²⁹ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ , examples of the ester group having 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, phenoxycarbonyl, acetoxy and propionyl. Examples thereof include oxy, butyryloxy, chloroacetyloxy, dichloroacetyloxy, trichloroacetyloxy, trifluoroacetyloxy, t-butylcarbonyloxy, methoxyacetyloxy, benzoyloxy and the like.

The ratio of the cationic polymerization initiator (B) to the cationically polymerizable component (A) is preferably 1 to 10 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the cationically polymerizable component (A). It is 2 to 8 parts by mass. If it is too small, curing tends to be insufficient, and if it is too large, it may adversely affect various physical properties such as the water absorption rate of the cured product and the strength of the cured product.

Further, a sensitizer and / or a sensitizer aid can be used in the curable composition of the present invention, if necessary. The sensitizer is a compound that exhibits maximum absorption at a wavelength longer than the maximum absorption wavelength indicated by the cationic polymerization initiator (B) and promotes the polymerization initiation reaction by the cationic polymerization initiator (B). The sensitizer is a compound that further promotes the action of the sensitizer.

Examples of the sensitizer and the sensitizing aid include anthracene-based compounds and naphthalene-based compounds.

Examples of the anthracene-based compound include those represented by the following formula (7).

ここで、式（７）中、Ｒ^５０およびＲ^５１は、各々独立に水素原子、炭素原子数１～６のアルキル基または炭素原子数２～１２のアルコキシアルキル基を表し、Ｒ^５２は水素原子または炭素原子数１～６のアルキル基を表す。

Here, in the formula (7), R ⁵⁰ and R ⁵¹ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ⁵² is a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.

Specific examples of the anthracene-based compound represented by the formula (7) include the following compounds.

For example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9,10-bis (2-butoxyethoxy) anthracene, 9,10 -Bis (3-butoxypropoxy) anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2- Ethyl-9,10-dipropoxyanthracene, 2-methyl- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl-or Examples thereof include 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene.

Examples of the naphthalene-based compound include those represented by the following formula (8).

ここで、式（８）中、Ｒ^５３およびＲ^５４は各々独立に炭素原子数１～６のアルキル基を表す。

Here, in the formula (8), R ⁵³ and R ⁵⁴ each independently represent an alkyl group having 1 to 6 carbon atoms.

Specific examples of the naphthalene-based compound represented by the formula (8) include the following compounds.

For example, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, Examples thereof include 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene and 1,4-dibutoxynaphthalene.

The ratio of the sensitizer and the sensitizer to the cationically polymerizable component (A) is not particularly limited, and the sensitizer and the sensitizing aid may be used at a generally normal ratio within a range that does not impair the object of the present invention. From the viewpoint of improving curability, it is preferable that the sensitizer and the sensitizing aid are each 0.1 to 3 parts by mass with respect to 100 parts by weight of the polymerizable component (A).

A silane coupling agent can be used in the curable composition of the present invention, if necessary. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkenyl-functional alkoxysilanes such as alkyl-functional alkoxysilanes, vinyltrichlorosilanes, vinyltrimethoxysilanes, vinyltriethoxysilanes, allyltrimethoxysilanes, 3-methacryloxybropyrtriethoxysilanes, 3-methacryloxybropyrtrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Β- (3,4-epylcyclohexyl) ethyltrimethoxysilane and other epoxy functional alkoxysilanes, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl -Amino-functional alkoxysilanes such as γ-aminopropyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium alkoxides such as titaniumtetraisopropoxide, titaniumtetranormalbutoxide, and titanium diocties. Titanium chelate such as ropylbis (octylene glycolate) and titanium diisopropoxybis (ethylacetacetate), zirconium tetraacetylacetonate, zirconium chelate such as zirconium tributoxymonoacetylacetonate, zirconium tributoxymono Zyryl acylates such as stearate, isocyanate silanes such as methyltriisocyanate silane, and the like can be used.

The amount of the silane coupling agent used is not particularly limited, but is usually in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the solid matter in the curable composition.

If necessary, a thermoplastic organic polymer may be used in the curable composition of the present invention to improve the properties of the cured product. Examples of the thermoplastic organic polymer include polystyrene, polymethylmethacrylate, methylmethacrylateethylacrylate copolymer, methylmethacrylateglycidylmethacrylate copolymer, poly (meth) acrylic acid, and styrene- (meth) acrylic acid copolymer. Examples thereof include (meth) acrylic acid-methyl methacrylate copolymer, glycidyl (meth) acrylate-polymethyl (meth) acrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester and the like.

The curable composition of the present invention is not particularly limited, and a solvent capable of dissolving or dispersing each of the above-mentioned components (A) and (B), which is usually used, can be used. Examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 , 2-Diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, -n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, succinic acid Ester-based solvents such as dimethyl and texanol; Cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol. Aether ester type such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. Solvents; BTX-based solvents such as benzene, toluene, xylene; aliphatic hydrocarbon-based solvents such as hexane, heptane, octane, cyclohexane; terpene-based hydrocarbon oils such as terepine oil, D-limonen, pinen; mineral spirit, swazole # Paraffin-based solvents such as 310 (manufactured by Cosmo Matsuyama Oil Co., Ltd.) and Solbesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane Solvents: Halogenized aromatic hydrocarbon solvents such as chlorobenzene; propylene carbonate, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, water and the like. These solvents can be used as one kind or a mixed solvent of two or more kinds.

Since the curable composition of the present invention improves curability, adhesion, and liquid storage stability, the water content is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. If there is too much water, it may become cloudy or the components may precipitate, which is not preferable.

If necessary, the curable composition of the present invention is further activated by desorbing the protecting group by an ultraviolet absorber, heating to a predetermined temperature, light irradiation, acid, etc., which are inactive at room temperature. It is also possible to use a compound that exhibits the ability to absorb ultraviolet rays.

Further, as long as the effects of the present invention are not impaired, radically polymerizable monomers, radical polymerization initiators, polyols, inorganic fillers, organic fillers, pigments, colorants such as dyes, defoaming agents, thickeners, etc. Surfactants, leveling agents, flame retardants, chixo agents, diluents, plasticizers, stabilizers, polymerization inhibitors, UV absorbers, antioxidants, antistatic agents, flow modifiers, adhesion promoters, etc. Various resin additives and the like can be added.

The curable composition of the present invention is applied on a support substrate by a known means such as a roll coater, a curtain coater, various types of printing, and dipping. Further, it is also possible to apply it once on a support substrate such as a film and then transfer it onto another support substrate, and there is no limitation on the application method thereof.

The material of the support substrate is not particularly limited, and a commonly used material can be used, for example, an inorganic material such as glass; diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl. Cellulose esters such as cellulose and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxy Polyesters such as ethane-4,4'-dicarboxylate, polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene and polymethylpentene; vinyl compounds such as polyvinyl acetate, polyvinyl chloride and polyvinyl fluoride; polymethylmethacrylate , Polyacrylate and the like; Acrylic resin; Polyethylene; Polysulfone; Polyether sulfone; Polyetherketone; Polyetherimide; Polyoxyethylene, Norbornen resin, Cycloolefin polymer (COP) and other polymer materials. The support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

In the method of curing the curable composition of the present invention by irradiation with energy rays, examples of the energy rays include ultraviolet rays, electron beams, X-rays, radiation, high frequencies and the like, and ultraviolet rays are most economically preferable. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, a xenon laser, and a metal halide lamp.

The conditions in the method for curing the curable composition of the present invention by heating are 70 to 250 ° C. for 1 to 100 minutes. After pre-baking (PAB; Pre-exposure bake), it may be pressurized and post-baked (PEB; Post exposure bake), or it may be baked at several different temperature steps. The heating conditions vary depending on the type and mixing ratio of each component, but are, for example, 70 to 180 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, a cured film can be obtained by heat-treating the coating film at 180 to 250 ° C., preferably 200 to 250 ° C. for 30 to 90 minutes in an oven and 5 to 30 minutes in a hot plate.

Specific uses of the curable composition of the present invention or a cured product thereof include adhesives, adhesives for polarizing plates, glasses, optical materials typified by imaging lenses, paints, coating agents, lining agents, inks, and the like. For resists, liquid resists, printing plates, color TVs, PC monitors, mobile information terminals, digital cameras, organic EL, display elements such as touch panels, insulating varnish, insulating sheets, laminated boards, printed boards, for semiconductor devices / for LED packages / Sealants for liquid crystal injection ports, organic EL, optical elements, electrical insulation, electronic parts, separation films, etc., molding materials, putties, glass fiber impregnants, sealants, semiconductors, solar cells Passion film, interlayer insulating film, protective film, prism lens sheet used for backlight of liquid crystal display device, Frenel lens sheet used for screen of projection TV, lens part of lens sheet such as wrenchular lens sheet, etc. Alternatively, examples thereof include an optical lens such as a microlens, an optical element, an optical connector, an optical waveguide, a casting agent for optical modeling, and the like, such as a backlight using such a sheet.

The display device of the present invention includes a transparent support, an undercoat layer, an antireflection layer, a polarizing element layer, a retardation layer, a birefringence layer, a light scattering layer, a hard coat layer, a lubricating layer, and a protective layer, if necessary. Examples thereof include those provided with each layer such as, and a film made of the cured product of the present invention can be used for each layer.

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples.

[Examples 1 to 16, Comparative Examples 1 to 7]
Each component was sufficiently mixed with the formulations shown in the following [Table 1] to [Table 3] to obtain a curable composition of Examples 1 to 16 and a curable composition of Comparative Examples 1 to 7, respectively. The unit of Examples and Comparative Examples is parts by mass.

As the cationically polymerizable component (A), the following compounds A1-1 to A1-5, A2-1 to A2-2, A3-1, A4-1 and A5-1 were used.
Compound A1-1: Bisphenol type diglycidyl ether compound A1-2: ADEKA Glycyrrol ED-509S (monofunctional aromatic epoxy compound manufactured by ADEKA Corporation)
Compound A1-3: ADEKA Glycyrrol ED-501 (monofunctional aromatic epoxy compound manufactured by ADEKA Corporation)
Compound A1-4: Orthoallylphenyl glycidyl ether compound A1-5: Orthophenylphenol glycidyl ether compound A2-1: Neopentyl glycol diglycidyl ether compound A2-2: 1,4-butanediol diglycidyl ether compound A3-1: Aron Oxetan OXT-221 (manufactured by Toa Synthetic Co., Ltd.)
Compound A4-1: Copolymer of 75 parts by mass of methyl methacrylate and 25 parts by mass of glycidyl methacrylate (weight average molecular weight 7,000)
Compound A5-1: Celoxide 2021P (alicyclic epoxy compound manufactured by Daicel Corporation)
Compound A5-2: Limonene dioxide

The following compound (B-1) was used as the cationic polymerization initiator (B).
Compound B-1: A 50% propylene carbonate solution of a mixture of the compound represented by the following formula (9) and the compound represented by the following formula (10).

(Adhesion)
The curable compositions of Examples 1 to 16 and Comparative Examples 1 to 7 obtained above were applied to one PMMA film (Sumitomo Chemical Co., Ltd .: Technoroy 125S001), and then another corona discharge was applied. A treated COP (cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd .: product number Zeonoa film 14-060) film and a laminator are used to bond them together, and a non-electrode ultraviolet light lamp is used to emit light equivalent to 1000 mJ / cm ² . A test piece was obtained by irradiating through a COP film and adhering. The obtained test piece was subjected to a 90-degree peel test. A curable composition having an adhesiveness of 1.0 N / cm or more can be used as an adhesive for a polarizing plate, preferably an adhesiveness of 2.0 N / cm or more, more preferably 3.0 N / cm / cm. It is cm or more. The obtained results are also shown in Tables 1 to 3.

(Curability)
When making the above test piece, the curability was also confirmed. Those whose coated surface was tack-free immediately after irradiation were evaluated as ++, those which became tack-free after 5 minutes were evaluated as +, and those whose tack remained even after 15 minutes were evaluated as-. A curable composition having a curability of ++ or + can be used as an adhesive for a polarizing plate, and a curable composition having a curability of ++ can be used particularly preferably as an adhesive for a polarizing plate, and the curability is-curing. The sex composition cannot be used as an adhesive for a polarizing plate. The obtained results are also shown in Tables 1 to 3.

(Paintability)
The curable compositions of Examples 1 to 16 and Comparative Examples 1 to 7 were each applied to one PMMA film (Sumitomo Chemical Co., Ltd .: Technoroy 125S001), and then another COP subjected to corona discharge treatment. (Cycloolefin polymer, manufactured by Nippon Zeon Co., Ltd .: Part number Zeonoa film 14-060) A film and a laminator are used to bond them together, and an electrodeless ultraviolet light lamp is used to irradiate light equivalent to 1000 mJ / cm ² through the COP film. And adhered to obtain a test piece. The appearance of the obtained sample was observed, and those without irregularities and bubbles were marked with ◯, and those with irregularities and bubbles were marked with x. A curable composition having a coatability of ◯ can be used as an adhesive for a polarizing plate, and a curable composition having a coatability of × cannot be used as an adhesive for a polarizing plate.

From [Table 1] to [Table 3], it is clear that the curable composition of the present invention has excellent adhesion to the cured product.

Claims (7)

In a curable composition containing 100 parts by mass of a cationically polymerizable component (A) and 1 to 10 parts by mass of a cationic polymerization initiator (B).
The cationically polymerizable component (A) has an aromatic epoxy compound (A1), an aliphatic glycidyl compound (A2), an oxetane compound (A3), and a cationically polymerizable substituent, and has a weight average molecular weight of 1,000 to 30. The aromatic epoxy compound (A1) is the main component of the cationically polymerizable component (A), and the polymer (A4) which is 000 is an essential component, and the polyfunctional aromatic epoxy compound and the monofunctional aromatic compound. Contains epoxy compounds ,
The polymer (A4) having a cationically polymerizable substituent and having a weight average molecular weight of 1,000 to 30,000 monopolymerizes or monopolymerizes a compound having a cationically polymerizable substituent on the side chain and having an ethylenically unsaturated bond. It is obtained by copolymerization, and the cationically polymerizable substituent is an epoxy group or an oxetane group.
A curable composition , wherein the monofunctional aromatic epoxy compound in the aromatic epoxy compound (A1) is 30 to 50 parts by mass with respect to 100 parts by mass of the polyfunctional aromatic epoxy compound . The curable composition according to claim 1, further comprising an alicyclic epoxy compound (A5) as the cationically polymerizable component (A). The curable composition according to claim 1, wherein the oxetane compound (A3) is a polyfunctional oxetane compound. The curable composition according to claim 2, wherein the oxetane compound (A3) is a polyfunctional oxetane compound. A method for curing a curable composition, which comprises irradiating the curable composition according to any one of claims 1 to 4 with active energy rays. A method for curing a curable composition, which comprises heating the curable composition according to any one of claims 1 to 4. A cured product according to any one of claims 1 to 4, which is a cured product of the curable composition.